The present invention relates to new 2-phenyl-methoxyimino-glyoxylic acid derivatives having microbicidal, insecticidal and acaricidal activity, a process for the preparation thereof, new intermediates for the preparation thereof, agrochemical compositions containing these active ingredients, as well as their usage in the control and prevention of plant-pathogenic fungi, acarids and insects in agriculture and in the field of hygiene.
The new compounds correspond to formula I 
wherein
A is a group OCHR4 or Nxe2x95x90CR4;
Y is O or NH,
R1 is C1-C6-alkyl;
R2 is C1-C6-alkyl or C1-C6-alkyl substituted by 1 to 5 fluorine atoms;
R3 is C1-C6-alkyl, C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C2-C6-alkynyloxy, C1-C6-alkoxycarbonyl, CN or halogen, whereby the above-mentioned groups, with the exception of CN and halogen, may be substituted by one or more identical or different substitutents selected from the group comprising halogen, cyano, nitro, C1-C6-alkoxycarbonyl, C1-C6-alkoxy, C1-C6-alkylthio, aminocarbonyl, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C2-C6-alkenyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, heteroaryl, heteroaryloxy, whereby the cyclic radicals in turn may be substituted by one or more identical or different substitutents selected from the group comprising halogen, cyano, nitro, C1-C6-alkyl, C1-C6halogenoalkyl, C1-C6-alkoxy, C1-C6-halogenoalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C2-C6-alkenyl, optionally substituted benzyl, optionally substituted benzyloxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted heteroaryl and optionally substituted heteroaryloxy, whereby the optionally substituted aromatic groups are unsubstituted or mono- to tri-substituted by the same or different substituents selected from halogen, C1-C6-alkyl, C1-C6-halogenoalkyl, C1-C6-alkoxy, C1-C6-halogenoalkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C3-C6-alkynyloxy, C1-C6-alkoxycarbonyl, CN or OCN; or
R3 is aryl, heteroaryl, heterocyclyl, aryloxy, heteroaryloxy or heterocyclyloxy, whereby the above-mentioned groups may be substituted by one or more identical or different substitutents selected from the group comprising halogen, C1-C6-alkoxy, halogeno-C1-C6-alkoxy, C1-C6-alkylthio, halogeno-C1-C6-alkylthio, C1-C6-alkylsulfinyl, halogeno-C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, halogeno-C1-C6-alkylsulfonyl, C1-C6-alkylcarbonyl, halogeno-C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, halogeno-C1-C6-alkoxycarbonyl, C1-C6-alkylamino-carbonyl, di-(C1-C6-alkyl)-aminocarbonyl, whereby the alkyl groups may be identical or different, C1-C6-alkylaminothiocarbonyl, di-(C1-C6-alkyl)-aminothiocarbonyl, whereby the alkyl groups may be identical or different, C1-C6-alkylamino, di-(C1-C6-alkyl)-amino, NO2, an unsubstituted C1-C4-alkylenedioxy group or one which is substituted once to four times by C1-C4-alkyl and/or by halogen, or CN, SF3 and QR5;
Q is a direct bond, O, O(C1-C6-alkylene), (C1-C6-alkylene)O, S(xe2x95x90O)p, S(xe2x95x90O)p(C1-C6-alkylene), (C1-C6-alkylene)S(xe2x95x90O)p, C1-C8-alkylene, C2-C6-alkenylene or C2-C6-alkynylene;
R5 is a C2-C6-alkenyl or C2-C6-alkynyl group either unsubstituted or substituted by 1 to 3 halogen atoms, a (C1-C4-alkyl)3Si group, whereby the alkyl groups may be identical or different, CN, an unsubstituted or mono- to penta-substituted C3-C6-cycloalkyl, aryl, hetaryl or heterocyclyl group, whereby the substituents are selected from the group comprising halogen, C1-C6-alkyl, halogeno-C1-C6-alkyl, C1-C6-alkoxy, halogeno-C1-C6-alkoxy, phenoxy and CN;
p is 0, 1 or 2;
R4 is methyl, ethyl or cyclopropyl;
R6 is hydrogen or methyl.
Formula I should include all the possible isomeric forms, as well as mixtures, e.g. racemic mixtures, and any [E/Z] mixtures.
Alkylxe2x80x94as a group per se and as a structural element of other groups and compounds, such as halogenoalkyl, alkoxy and alkylthioxe2x80x94is either straight-chained, i.e. methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, e.g. isopropyl, isobutyl, sec.-butyl, tert.-butyl, isopentyl, neopentyl or isohexyl.
Alkenylxe2x80x94as a group per se se and as a structural element of other groups and compounds, such as halogenoalkenylxe2x80x94is either straight-chained, for example vinyl, 1-methylvinyl, allyl, 1-butenyl or 2-hexenyl, or branched, for example isopropenyl.
Alkynylxe2x80x94as a group per se and as a structural element of other groups and compounds, such as halogenoalkynylxe2x80x94is either straight-chained, for example propargyl, 2-butynyl or 5-hexynyl, or branched, for example 2-ethynylpropyl or 2-propargylisopropyl.
Alkylenedioxy is xe2x80x94O(alkylene)Oxe2x80x94.
Alkylenexe2x80x94as a group per se and as a structural element of other groups and compounds, such as O(alkylene), (alkylene)O, S(xe2x95x90O)p(alkylene), (alkylene)S(xe2x95x90O)p or alkylenedioxyxe2x80x94 is either straight-chained, for example xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2xe2x80x94 or xe2x80x94CH2CH2CH2CH2xe2x80x94, or branched, for example xe2x80x94CH(CH3)xe2x80x94, xe2x80x94CH(C2H5)xe2x80x94, xe2x80x94C(CH3)2xe2x80x94, xe2x80x94CH(CH3)CH2xe2x80x94 or xe2x80x94CH(CH3)CH(CH3)xe2x80x94.
Alkenylene is either straight-chained, for example vin-1,2-ylene, all-1,3-ylene, but-1-en-1,4-ylene or hex-2-en-1,6-ylene, or branched, for example 1-methylvin-1,2-ylene.
Alkynylene is either straight-chained, for example propargylene, 2-butynylene or 5-hexynylene, or branched, for example 2-ethynylpropylene or 2-propargylisopropylene.
Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Halogenoalkyl may contain indentical or different halogen atoms.
Aryl is phenyl or naphthyl, preferably phenyl.
Heteroaryl is a cyclic aromatic group with 5 to 9 ring members in one or two rings, 1 to 3 members of which are hetero atoms, selected from the group oxygen, sulphur and nitrogen. 1 to 2 benzene rings may be condensed onto the heterocycle, whereby the binding to the residual molecule takes place either via the hetero or the benzene moiety.
Examples are benzimidazolyl, benzisoxazolyl, benzisothiazolyl, benzocoumarinyl, benzofuryl, benzothiadiazolyl, benzothiazolyl, benzothienyl, benzoxazolyl, benzoxdiazolyl, quinazolinyl, quinolyl, quinoxalinyl, carbazolyl, dihydrobenzofuryl, furyl, imidazolyl, indazolyl, indolyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, ethylenedioxyphenyl, naphthyridinyl, oxazolyl, phenanthridinyl, phthalazinyl, pteridinyl, purinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyrazolo[3,4-b]pyridyl, pyridyl, pyrimidinyl, pyrrolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, thiazolyl, thienyl, triazinyl and triazolyl.
Pyridyl, pyrazinyl, pyrimidinyl, thiazolyl, quinolinyl and thienyl are preferred.
Heterocyclyl is a 5- to 7-membered non-aromatic ring with one to three hetero atoms selected from the group comprising N, O and S.
Aromatic 5- and 6-rings are preferred, which have a nitrogen atom as hetero atom and optionally a further hetero atom, preferably nitrogen or sulphur, especially nitrogen.
Thiazolinyl and oxazolinyl are preferred.
Of the compounds of formula I, those groups are preferred in which:
(1)
a) A is the group Nxe2x95x90CR4; or
b) R1 is methyl or ethyl, preferably methyl; or
c) R2 is methyl, ethyl, fluoromethyl or trifluoroethyl, preferably methyl; or
d) R3 is C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C3-C6-alkynyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkyloxy or C1-C6-alkoxycarbonyl, whereby the above-mentioned groups may be partially or totally halogenated; and also CN, OCN or halogen; or
e) R3 is phenyl which is unsubstituted or mono- to tri-substituted by identical or different subsituents from halogen, C1-C6-alkyl, C1-C6-halogenoalkyl, C1-C6-alkoxy, C1-C6-halogenoalkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C3-C6-alkynyloxy, C1-C6-alkoxycarbonyl, CN, OCN, optionally substituted benzyl, optionally substituted phenyl or optionally substituted phenoxy, whereby the optionally substituted aromatic groups are unsubstituted or mono- to tri-substituted by identical or different subsituents from halogen, C1-C6-alkyl, C1-C6-halogenoalkyl, C1-C6-alkoxy, C1-C6-halogenoalkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C3-C6-alkynyloxy, C1-C6-alkoxycarbonyl, CN or OCN; or
f) R3 is pyridyl, pyrimidinyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, which are unsubstituted or mono- to tri-substituted by identical or different subsituents from halogen, cyano, nitro, aminocarbonyl, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkylcarbonyl, C1-C4-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, optionally substituted arylcarbonyl, C1-C4-alkoxy, C1-C4-halogenoalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl or C2-C6-alkenyl; or
g) R4 is methyl; or
h) R6 is hydrogen.
(2) Compounds of formula I wherein:
A is Nxe2x95x90CR4;
Y is O or NH;
R1 is methyl or ethyl, preferably methyl;
R2 is C1-C6-alkyl or C1-C6-alkyl substituted by 1-5 fluorine atoms;
R3 is C1-C6-alkyl, C1-C6-alkoxy, C1-6-alkoxycarbonyl, CN, C3-C6-cycloalkyl, aryl, heteroaryl, heterocyclyl, aryloxy, heteroaryloxy or heterocyclyloxy, whereby, with the exception of CN, the above-mentioned groups may be substituted;
R4 is methyl, ethyl or cyclopropyl;
R6 is hydrogen or methyl.
(2a) Of the compounds mentioned under (2), in particular those wherein:
R2 is C1-C6-alkyl, fluoromethyl, difluoromethyl or 2,2,2-trifluoroethyl;
R3 is C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkoxycarbonyl, CN, C3-C6-cycloalkyl, phenyl which is unsubstituted or mono- to tri-substituted by halogen, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkoxy, C1-C4-halogenoalkoxy, C2-C4-alkenyl, C2-C4-alkenyloxy, C2-C6-alkynyl, C3-C6-alkynyloxy, CN, OCN, benzyl, phenyl, or phenyloxy, wherein these aromatic groups are unsubstituted or mono- or di-substituted by halogen, C1-C2-alkyl, C1-C2-halogenoalkyl or C1-C2-alkoxy.
(2b) Of the compounds mentioned under (2a), in particular those wherein:
R3 is C1-C4-alkyl, C1-C4-alkoxy, C1-C6-alkoxycarbonyl, or phenyl, which is unsubstituted or mono- to di-substituted by halogen, C1-C2-alkyl, C1-C2-halogenoalkyl, C1-C2-alkoxy.
(2c) Of the compounds mentioned under (2), in particular those wherein:
R3 is C1-C4-alkyl, C1-C4-alkoxy, C1-C6-alkoxycarbonyl, or phenyl, which is unsubstituted or mono- to di-substituted by halogen, C1-C2-alkyl, C1-C2-halogenoalkyl, C1-C2-alkoxy;
R4 is methyl;
R6 is methyl.
(3) Compounds of formula I, wherein:
A is OCHR4;
Y is O or NH;
is methyl or ethyl, preferably methyl;
R2 is C1-C6-alkyl, preferably methyl;
R3 is C1-6-alkyl, C1-6-halogenoalkyl, C2-C6-alkenyl, C1-6-alkoxy, C2-C6-alkenyloxy, C1-C6-alkoxycarbonyl, CN, C3-C6-cycloalkyl, aryl, heteroaryl, heterocyclyl, aryloxy, heteroaryloxy or heterocyclyloxy, whereby the hydrocarbon radicals and the cyclic radicals may be substituted as already mentioned above;
R4 is methyl, ethyl or cyclopropyl, preferably methyl;
R6 is hydrogen or methyl.
(3a) Of the compounds mentioned under (3), in particular those wherein:
R3 is C1-C6-alkyl, C1-C6-halogenoalkyl, C2-C6-alkenyl, C1-C6-alkoxy, C2-C6-alkenyloxy, C1-C6-alkoxycarbonyl, C3-C6-cycloalkyl;
R4 is methyl.
(3b) Of the compounds mentioned under (3), in particular those wherein:
R3 is phenyl which is unsubstituted or mono- or di-substituted by halogen, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkoxy, C1-C4-halogenoalkoxy, C2-C4-alkenyl, C2-C4-alkenyloxy, benzyl, phenyl, or phenyloxy, wherein these aromatic groups are unsubstituted or mono- or di-substituted by halogen, C1-C2-alkyl, C1-C2-halogenoalkyl or C1-C2-alkoxy;
R4 is methyl;
R6 is hydrogen or methyl.
(3c) Of the compounds mentioned under (3), in particular those wherein:
R4 and R6 are methyl.
In EP-A-596 254 certain methoximinoacetic acid derivatives have been proposed as agricultural fungicides which are based on a benzaldoxime structure
Compounds of formula I may be produced as follows:
A) A compound of formula I may be produced by reacting a compound of the general formula II 
xe2x80x83wherein A, R2 and R3 have the significances given for formula I, with an aldehyde or ketone of the general formula III or with one of its acetal derivatives of the general formula IV 
xe2x80x83wherein Y, R1 and R6 have the significances given for formula I, and R5 is C1-C6-alkyl or the two R5, together with the two oxygen atoms and the carbon to which they are bonded, form a cyclic acetal.
B) A compound of formula I, wherein Y is NH and A is Nxe2x95x90CR4, may be produced by reacting a hydrazone of the general formula V, 
xe2x80x83wherein R1 and R6 have the significances given for formula I, with an aldehyde or a ketone of the general formula VI, 
xe2x80x83wherein R2, R3 and R4 have the significances given for formula I.
C) A compound of formula I, wherein A is OCHR4, may be produced by reacting an oxime of the general formula VII 
xe2x80x83wherein Y, R1 and R6 have the significances given for formula I, with a halide of the general formula VIII 
xe2x80x83wherein R2, R3 and R4 have the significances given for formula I and Hal is a halogen atom such as chlorine, bromine or iodine, especially bromine.
D) A compound of formula I may be produced whereby an oxime of the general formula IX 
xe2x80x83wherein Y, R1, R3, R6 and A have the significances given for formula I (whereby R3 cannot be halogen), is etherified.
The compounds of formula IX may be obtained whereby either
a) a ketone of the general formula X 
xe2x80x83wherein A, Y, R2, R3 and R6 have the significances given for formula I, is reacted with hydroxylamine or with one of its salts, or
b) a compound of the general formula XI 
xe2x80x83wherein Y, R1, R3, R4 and R6 have the significances given for formula I, is reacted with nitrous acid or with an alkyl nitrite in the presence of an acid or base, or
c) an oxime of the general formula XII 
xe2x80x83wherein A and R3 have the significances given for formula I, is reacted with an aldehyde or ketone of the general formula III or with an acetal of the general formula IV, as described under A), or
d) a ketone oxime of the general formula XIII 
xe2x80x83wherein R3 and R4 have the significances given for formula I, is reacted with a hydrazone of the general formula V.
aa) A compound of formula X, wherein A is OCHR4 and Y, R3, R4 and R6 have the significances given for formula I, may be produced by reacting an oxime of formula VII with a halide of the general formula XXIV 
xe2x80x83wherein Hal is a halogen atom such as chlorine, bromine or iodine, especially bromine.
E) A compound of formula I may be produced by reacting a ketone of the general formula X with an alkoxyamine of the general formula XIV
R2xe2x80x94ONH2xe2x80x83xe2x80x83XIV
xe2x80x83wherein R2 has the significances given for formula I, or with one of its salts.
F) A compound of formula I may be produced by reacting an oxime derivative of the general formula XV 
xe2x80x83wherein A, Y, R1, R2, R3 and R6 have the significances given under formula I, with a methylating agent such as methyl iodide or dimethyl sulphate.
The compounds of formula XV may be obtained whereby either
a) a ketone of the general formula XVI 
xe2x80x83wherein A, Y, R1, R2, R3 and R6 have the significances given under formula I, is reacted with hydroxylamine or with one of its salts, or
b) a phenylacetic acid derivative of the general formula XVII 
xe2x80x83wherein A, Y, R1, R2, R3 and R6 have the significances given under formula I, is reacted with nitrous acid or with an alkyl nitrite.
c) A keto derivative of the general formula XVI, wherein Y is O, may be produced whereby an acyl cyanide of the general formula XVIII 
xe2x80x83wherein A, R2, R3 and R6 have the significances given under formula I, is reacted in a Pinner reaction with an alcohol of the general formula XIX
R1xe2x80x94OHxe2x80x83xe2x80x83XIX
xe2x80x83wherein R1 has the significances given under formula I.
d) A keto derivative of the general formula XVI, wherein Y is NH, may be produced whereby either
1) a keto derivative of the general formula XVI, wherein Y is O, is reacted with an alkylamine of the general formula XX
R1xe2x80x94NH2xe2x80x83xe2x80x83XX
xe2x80x83wherein R1 has the significances given under formula I, or
2) an acid chloride of the general formula XXI 
xe2x80x83wherein A, R2, R3 and R6 have the significances given under formula I, is reacted with an isocyanide of the general formula XXII
R1xe2x80x94NCxe2x80x83xe2x80x83XXII
xe2x80x83wherein R1 has the significances given under formula I (see EP 547825).
G) A compound of formula I may be produced by reacting a ketone of the general formula XVI, wherein A, Y, R1, R2, R3 and R6 have the significances given under formula I, with O-methylhydroxylamine or with one of its salts.
H) A compound of formula I, wherein Y is NH, may be produced by reacting an ester of the general formula I, wherein Y is O, with an alkylamine of the general formula XX
R1xe2x80x94NH2xe2x80x83xe2x80x83XX
xe2x80x83wherein R1 has the significances given under formula I.
I) A compound of formula I, wherein Y is NH, may be produced by reacting an oxime ether of the general formula XXIII in the presence of a ruthenium catalyst 
xe2x80x83wherein A, R1, R2, R3 and R6 have the significances given under formula I, with an oxidation agent, for example dimethyl sulphoxide/oxalyl chloride, iodosobenzene, optionally in the presence of a ruthenium catalyst, potassium permanganate, manganese dioxide, tert.-butyl hypochlorite, sodium hypochlorite, tert.-butyl hydroperoxide, N-methylmorpholine-N-oxide.
All the above-described reactions are known per se, for example from WO 96/38408 and EP-A-547.825.
The above-mentioned new intermediates were developed especially for the present invention and similarly form an object of this invention; those of formulae V, IX, X, XV, XVI, XVII, XVIII, XXI and XXIII are of particular importance.
The educts are known or may be produced by known methods.
The compounds of formula I may be used preventatively and/or curatively in the agrarian sector and related fields as active ingredients for controlling plant pests. The active ingredients of formula I according to the invention are notable for their good activity even at low concentrations, for their good plant tolerance and for their environmentally friendly nature. They have very advantageous, especially systemic, properties and may be used to protect a plurality of cultivated plants. Using the active ingredients of formula I on plants or plant parts (fruit, flowers, leaves, stems, tubers, roots) of various crops, the pests appearing can be controlled or destroyed, whereby the parts of plants which grow later also remain protected, e.g. from phytopathogenic micro-organisms.
The compounds I may additionally be used as a dressing to treat seeds (fruits, tubers, corms) and plant cuttings to protect against fungal infections and against phytopathogenic fungi occurring in the soil.
The compounds I are effective for example against the following classes of related phytopathogenic fungi: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria); Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia); Ascomycetes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and Oomycetes (e.g. Phytophthora, Pythium, Plasmopara).
Target crops for the plant-protecting usage in terms of the invention are for example the following plant cultivars: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pome, stone and berry fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); legumes (beans, lentils, peas, soya); oil crops (rape, mustard, poppy, olives, sunflowers, coconut, castor oil, cocoa, peanut); cucumber plants (squashes, cucumber, melons); fibre plants (cotton, flax, hemp, jute); citrus fruits (oranges, lemons, grapefruits, mandarines); vegetables (spinach, lettuce, asparagus, cabbage varieties, carrots, onions, tomatoes, potatoes, paprika); laurels (avocado, cinnamonium, camphor) and plants such as tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamental plants.
In addition, the compounds of formula I according to the invention are valuable active ingredients against insects and pests of the order Acarina, as are present on crop plants and ornamentals in agriculture and in horticulture and in woodland, whilst being tolerated by mammals, fish and plants. The compounds of formula I are especially suitable for the control of pests in crops of cotton, vegetables, fruit and rice, for example spider mites, aphids, caterpillars and plant- and leaf-hoppers in rice. The pests primarily controlled are spider mites such as Panonychus ulmi, aphids such as Aphis craccivora, caterpillars such as those of Heliothis virescens and plant- and leaf-hoppers in rice such as Nilaparvata lugens or Nephotettix cincticeps. 
The good pesticidal activity of the compounds I according to the invention corresponds to a mortality of at least 50-60% of the pests mentioned.
Further areas of application for the active ingredients according to the invention are the protection of stores and material, where the storage matter is protected against putrescence and mould, as well as against insect pests (e.g. corn weevils, mites, maggots etc.). In the hygiene sector, compounds of formula I successfully control animal parasites such as ticks, mites, warble flies etc. on domestic and farm animals. The compounds I are effective against individual or collective stages of development of normally sensitive, but also resistant species of pest. Their activity may be demonstrated in this case for example by the mortality of pests which appear directly or only after some time, for example during moulting, or by reduced oviposition and/or hatching rate.
The compounds I are used in unchanged form or preferably together with customary excipients in formulation techniques. To this end, they are conveniently processed in known manner e.g. into emulsion concentrates, coatable pastes, directly sprayable or diluable solutions, diluted emulsions, wettable poweders, soluble powders, dusts or granules, e.g. by encapsulation into for example polymeric materials. As with the type of medium, the application processes, such as spraying, atomizing, dusting, scattering, coating or pouring are similarly chosen according to the desired aims and the prevailing conditions.
Suitable substrates and additives may be solid or liquid and are useful substances in formulation techniques, e.g. natural or regenerated mineral substances, dissolving aids, dispersants, wetting agents, tackifiers, thickeners, binding agents or fertilizers.
The compounds of formula I may be mixed with further active ingredients, e.g. fertilizers, ingredients providing trace elements or other plant protection compositions, especially further fungicides. In doing so, unexpected synergistic effects may occur.
Preferred additions to the mixture are:
Azoles, such as azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole;
pyrimidinyl carbinole, such as ancymidol, fenarimol, nuarimol;
2-amino-pyrimidines, such as bupirimate, dimethirimol, ethirimol;
morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamin, tridemorph;
anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil;
pyrroles, such as fenpiclonil, fludioxonil;
phenylamides, such as benalaxyl, furalaxyl, metalaxyl, r-metalaxyl, ofurace, oxadixyl;
benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole;
dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozoline;
carboxamides, such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, thifluzamide;
guanidines, such as guazatine, dodine, iminoctadine;
strobilurines, such as azoxystrobin, kresoxim-methyl, metominostrobin, SSF-129, trifloxystrobin;
dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram;
N-halomethylthio, such as captafol, captan, dichlofluanid, fluoromides, folpet, tolyfluanid;
Cu compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper;
nitrophenol-derivatives, such as dinocap, nitrothal-isopropyl;
organo-p-derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, toiclofos-methyl;
Various others, such as acibenzolar-S-methyl, anilazine, blasticidin-S, chinomethionate, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, fenamidone, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb, IKF-916, kasugamycin, methasulfocarb, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin.
One preferred method of application of an active ingredient of formula I or of an agrochemical composition containing at least one of these active ingredients is foliar application. The frequency and amount of application depend on the severity of the attack by the pathogen in question. However, the active ingredients I may also reach the plants through the root system via the soil (systemic action) by drenching the locus of the plant with a liquid preparation or by incorporating the substances into the soil in solid form, e.g. in the form of granules (soil application). In rice cultivations, these granules may be dispensed over the flooded paddy field. The compounds I may however also be applied to seed grain to treat seed material (coating), whereby the grains or tubers are either drenched in a liquid preparation of the active ingredient or coated with a solid preparation.
The compositions are produced in known manner, e.g. by intimately mixing and/or grinding the active ingredient with extenders such as solvents, solid carriers and optionally surfactants.
The agrochemical compositions normally contain 0.1 to 99 percent by weight, especially 0.1 to 95 percent by weight, of active ingredient of formula I, 99.9 to 1 percent by weight, especially 99.8 to 5 percent by weight, of a solid or liquid additive and 0 to 25 percent by weight, especially 0.1 to 25 percent by weight, of a surfactant.
Favourable application rates are in general 1 g to 2 kg of active substance (AS) per hectare (ha), preferably 10 g to 1 kg AS/ha, especially 20 g to 600 g AS/ha. For usage as a seed dressing, it is advantageous to use dosages of 10 mg to 1 g active substance per kg of seed grain.
While concentrated compositions are preferred for commercial usage, the end user normally uses diluted compositions.
The compositions may also contain further additives, such as stabilizers, anti-foaming agents, viscosity regulators, binding agents or tackifiers, as well as fertilizers or other active ingredients to achieve special effects.